Optical frequency comb-based measurements and the revisited assignment of high-resolution spectra of CH2Br2 in the 2960 to 3120 cm−1 region

Abstract

Brominated organic compounds are toxic ocean-derived trace gases that affect the oxidation capacity of the atmosphere and contribute to its bromine burden. Quantitative spectroscopic detection of these gases is limited by the lack of accurate absorption cross-section data as well as rigorous spectroscopic models. This work presents measurements of high-resolution spectra of dibromomethane, CH₂Br₂, from 2960 cm⁻¹ to 3120 cm⁻¹ by two optical frequency comb-based methods, Fourier transform spectroscopy and a spatially dispersive method based on a virtually imaged phased array. The integrated absorption cross-sections measured using the two spectrometers are in excellent agreement with each other within 4%. A revisited rovibrational assignment of the measured spectra is introduced, in which the progressions of features are attributed to hot bands rather than different isotopologues as was previously done. Overall, twelve vibrational transitions, four for each of the three isotopologues CH₂⁸¹Br₂, CH₂⁷⁹Br⁸¹Br, and CH₂⁷⁹Br₂, are assigned. These four vibrational transitions are attributed to the fundamental ν₆ band and the nearby nν₄ + ν₆ − nν₄ hot bands (with n = 1–3) due to the population of the low-lying ν₄ mode of the Br–C–Br bending vibration at room temperature. The new simulations show very good agreement in intensities with the experiment as predicted by the Boltzmann distribution factor. The spectra of the fundamental and the hot bands show progressions of strong Q_Ka(J) rovibrational sub-clusters. The band heads of these sub-clusters are assigned and fitted to the measured spectra, providing accurate band origins and the rotational constants for the twelve states with an average error of 0.0084 cm⁻¹. A detailed fit of the ν₆ band of the CH₂⁷⁹Br⁸¹Br isotopologue is commenced after assigning 1808 partially resolved rovibrational lines, with the band origin, rotational, and centrifugal constants as fit parameters, resulting in an average error of 0.0011 cm⁻¹.